KR101487543B1 - Adsorption materials of carbon dioxide using cross-linking reaction of amine and its application. - Google Patents

Abstract

A method for producing a completely organic carbon dioxide adsorbent is presented. As a method for realizing this, a polyfunctional epoxy is used as a curing agent for an amine, and a part of the -NH ₂ and -NH functional groups in the amine chain are subjected to a ring opening reaction to partially cure the amine in a liquid or high viscosity liquid form, .
In order to improve and optimize the carbon dioxide adsorption performance, it is possible to control the degree of curing and maximize the amount of carbon dioxide adsorption by adjusting the kind of amine, structure, molecular weight, etc. and mixing ratio with various curing agents.
The present invention provides a dry adsorbent having a simple carbon dioxide adsorption ability while having a simple manufacturing process and a low unit cost by a technique related to the synthesis of a new concept of dry adsorbent.
In addition, a carrier such as mesoporous silica is not required, and crosslinking reaction of amines is not required. Therefore, there is no problem of dissolving in water and organic solvent and not eluting. Production of carbon dioxide adsorbing material capable of blending with commercial polymers, extrusion, It is possible to overcome all the problems of the conventional adsorbent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a carbon dioxide adsorbing material using amine crosslinking reaction,

The present invention relates to a material which can be used as a carbon dioxide adsorbent and a method of using the same, wherein a fluid amine chain and a crosslinker having an epoxy functional group form a cured amine polymer of a three-dimensional network structure through mutual reaction Technology.

Carbon dioxide (CO ₂ ) is a typical greenhouse gas and is needed for removing and recovering carbon dioxide from a plant that discharges a large amount of carbon dioxide, such as thermal power plants. In addition, it will be necessary to remove carbon dioxide through breathing in indoor, underground, and automobile interior where carbon dioxide concentration should be kept below a certain level.

In addition, since 30 vol% of carbon dioxide is generated from the biogas generated in the sewage treatment plant and the landfill, high-performance carbon dioxide absorbent is essential to purify methane gas of high purity from the biogas.

Since the era of industrialization, the concentration of greenhouse gases on the earth has increased rapidly due to the increase in the use of fossil fuels. The greenhouse gas concentration of the Earth's atmosphere is 450 CO ₂ eq. ppm, and the carbon dioxide concentration is about 375 ppm, which is about 35% increase over the past 100 years, showing a steep rise of about 0.4% per year.

Corresponding to the Convention on Climate Change The field of greenhouse gas abatement technology development is mostly in the greenhouse gas sector and focuses on controllable carbon dioxide reduction. The International Energy Agency (IEA) predicts that carbon dioxide capture and storage (CCS) can reduce carbon dioxide by about 22%, a way to reduce carbon dioxide. The cost of recovering carbon dioxide in the CCS technology accounts for about 75 to 85% of the total, which requires more economical process development. The process of removing low-concentration carbon dioxide contained in the combustion exhaust gas from a power plant is called a post-combustion process. The process is divided into a wet absorption method and a dry adsorption method.

Conventional carbon dioxide recovery methods include absorption method, adsorption method, membrane separation method, and industrially, absorption method is most widely used.

Wet recovery requires not only periodic replenishment of the absorption solution but also much effort for maintenance such as erosion of the equipment and generation of secondary pollutants.

The membrane separation method utilizes the permeability and selectivity of the constituent gas components and selectively separates the carbon dioxide in the mixed gas. By solving only a few problems such as the development of a wide separation membrane, the selectivity of the membrane and the improvement of durability, However, the method is still very inadequate.

  Since the dry adsorption method has a low pressure loss of the fluid and can constitute the apparatus compact, an economical carbon dioxide recovery process can be realized. In addition, the absorption method has a higher energy consumption than the absorption method, but the apparatus is relatively simple and has little influence on the surrounding environment by the dry method.

Laid-Open Patent Application No. 2013-0047256 relates to a solid carbon dioxide absorbent containing amine or a compound thereof for dry carbon dioxide capture process and a method for producing the solid carbon dioxide absorbent, and a solid absorbent applied to a dry- In the process of continuously circulating the reactor, the sorption capacity is high, the sorption rate is fast, the exhaust gas or gas stream conditions are met, the CO2 can be removed to a low concentration, To high purity CO2. In addition, the solid absorbent satisfies the characteristics of having physical abrasion such as inter-particle collision, friction, breakage or cracking in the process of circulating between two reactors, and chemical abrasion loss due to volume expansion and shrinkage due to chemical reaction A porous carrier capable of satisfying the physicochemical requirements of the absorbent is prepared by using a spray-drying method, and an absorbent on which the amine compound is supported on the carrier is prepared. A method for producing a carbon dioxide absorbent comprises the steps of: preparing a slurry composition comprising a support composition and a solvent containing a support and an inorganic binder; spray-drying the slurry composition to prepare solid particles; Calcining the resultant to form a carrier, and supporting the amine compound on the pores of the carrier. However, there is still a need to overcome the problem of difficulty in selectively adsorbing carbon dioxide, which is a problem of the conventional dry adsorbent, and the phenomenon that the amine is eluted because there is no chemical bond between mesoporous silica carrier and amine.

As a dry adsorbent of carbon dioxide, an adsorbent using pores such as alumina, silica gel, activated carbon, zeolite and the like is used, but such a dry adsorbent has difficulty in selectively adsorbing carbon dioxide.

In order to overcome this problem, a dry adsorbent manufactured by a new process is prepared by impregnating a mesoporous silica (pore size: 2 to 50 nm) carrier with an amine selectively chemically adsorbing only carbon dioxide. The adsorbent has a very high ability to adsorb carbon dioxide (3 mmol CO2 / g-sorbent or more), the production process of mesoporous silica is difficult, and a large amount of surfactant is calcined in the production of mesoporous silica to generate carbon dioxide.

In addition, the amine used in the carbon dioxide adsorbing material using the mesoporous silica carrier is a simple physical impregnation without chemical bonding, so that it dissolves in the organic solvent, and the amine flows out of the pores of the carrier over time.

As a result, the adsorbent material can not be blended, extruded, or injected with a commercial polymer, and thus can not be formed into a desired shape.

In order to solve such problems, the present invention proposes a method of manufacturing a completely organic carbon dioxide adsorbent in which carriers such as mesoporous silica, fumed silica and silica particles are completely excluded.

As a method for realizing this, a multifunctional epoxy is introduced as a curing agent for an amine. A solid carbon dioxide adsorbing material can be prepared by partially hydrogenating a liquid or highly viscous amine in a ring-opening reaction of some of the -NH ₂ and -NH functional groups in the amine chain using the polyfunctional epoxy.

In order to improve and optimize the carbon dioxide adsorption performance, it is possible to control the degree of curing and maximize the amount of carbon dioxide adsorption by adjusting the kind of amine, structure, molecular weight, etc. and mixing ratio with various curing agents.

Examples of amines applicable to the present invention include the use of all kinds of amines containing at least one functional group of R ₁ -NH ₂ , R ₁ -N (R ₂ ) H and R ₁ -N (R ₂ ) -R ₃ This is possible.

Various methods for synthesizing a carbon dioxide adsorbing material include a method of dissolving an amine and a polyfunctional epoxy in methanol using a solvent, and then increasing the temperature of the mixed solution to 80 ° C or higher to proceed the crosslinking reaction.

The advantage of this reaction is that all materials can be homogeneously mixed with methanol to give a uniform and even crosslinking reaction.

Alternatively, it is possible to perform a crosslinking reaction in a bulk state without using a solvent. In this method, it is also possible to apply a batch type in which all materials are put into a container and mixed and the temperature is raised in the oven to perform crosslinking.

In addition, both of the twin extruders can be used to form a master batch by continuously feeding a material at a constant rate and performing a crosslinking reaction.

The present invention provides a dry adsorbent having a carbon dioxide adsorption capacity of 2 mmol CO ₂ / g-sorbent with a simple manufacturing process and a low unit cost, which is related to the synthesis of a new concept of dry adsorbent.

In addition, a carrier such as mesoporous silica is not required, and crosslinking reaction of amines is not required. Therefore, there is no problem of dissolving in water and organic solvent and not eluting. Production of carbon dioxide adsorbing material capable of blending with commercial polymers, extrusion, It is possible to overcome all the problems of the conventional adsorbent.

Figure 1 shows a conventional dry adsorbent manufacturing process.
2 shows amines having a carbon dioxide adsorption function according to an embodiment of the present invention.
Figure 3 shows various curing agents for amine adsorbents according to embodiments of the present invention.
FIG. 4 is a schematic view of a completely organic-based carbon dioxide adsorbent manufactured by curing an amine adsorbent according to an embodiment of the present invention.
Figure 5 shows the FTIR spectra of PEI 10K, PEGDE and Crosslinked PEI (C-PEI) according to embodiments of the present invention.
6 is a TEM photograph (A) of Crosslinked PEI (C-PEI) according to an embodiment of the present invention. Crosslinked PEI (C-PEI) (1: 3) ).
7 shows a SEM of Crosslinked PEI (C-PEI) (1: 6) according to an embodiment of the present invention.
8 shows carbon dioxide adsorption curves for Crosslinked PEI (C-PEI) 1: 2, 1: 3 and 1: 6 at 75 ° C according to an embodiment of the present invention.
9 shows carbon dioxide adsorption curves for Crosslinked PEI (C-PEI) 1: 3, 1: 6 at 35 ° C according to an embodiment of the present invention.
10 is a schematic diagram of a twin extruder process according to an embodiment of the present invention.
11 shows a digital photograph of a master batch according to an embodiment of the present invention.
12 shows a method for producing carbon dioxide (CO ₂ ) adsorbing material using a crosslinking reaction of an amine according to an embodiment of the present invention.
FIG. 13 shows a method for producing a carbon dioxide (CO ₂ ) adsorbing material using a crosslinking reaction of an amine according to another embodiment of the present invention.

Figure 1 shows a conventional dry adsorbent manufacturing process.

As the dry adsorbent of carbon dioxide carbon dioxide (CO ₂ ), pore-based adsorbents such as alumina, silica gel, activated carbon, zeolite and the like are used. However, such dry adsorbents have difficulty in selectively adsorbing carbon dioxide.

In order to overcome this problem, a dry adsorbent manufactured by a new process is prepared by impregnating a mesoporous silica (pore size: 2 to 50 nm) carrier with an amine selectively chemically adsorbing only carbon dioxide. The adsorbent has a very high ability to adsorb carbon dioxide (3 mmol CO2 / g-sorbent or more), the production process of mesoporous silica is difficult, and a large amount of surfactant is calcined in the production of mesoporous silica to generate carbon dioxide.

In addition, the amine used in the carbon dioxide adsorbing material using the mesoporous silica carrier is a simple physical impregnation without chemical bonding, so that it dissolves in the organic solvent, and the amine flows out of the pores of the carrier over time.

As a result, the adsorbent material can not be blended, extruded, or injected with a commercial polymer, and thus can not be formed into a desired shape.

In order to solve such a problem, in the present invention, by using a technique of forming a cured amine polymer of a three-dimensional network structure through a mutual reaction between a fluid amine chain and a cross linker having an epoxy functional group, (CO ₂ ) adsorbent material.

12 shows a method for producing carbon dioxide (CO ₂ ) adsorbing material using a crosslinking reaction of an amine according to an embodiment of the present invention.

A method for producing a carbon dioxide (CO ₂ ) adsorbent material using a crosslinking reaction of an amine, comprising the steps of: preparing an amine and a curing agent; mixing the amine and the curing agent to prepare a mixture; Adding the mixture to an oven and allowing the mixture to react; removing the unreacted material using methanol after completion of the reaction; and drying the unreacted material.

The amine is an amine containing at least one functional group selected from the group consisting of R ₁ -NH ₂ , R ₁ -N (R ₂ ) H and R ₁ -N (R ₂ ) -R _3. Polyethylenimine, Tetraethylenepentamine , Triethylenetetramine, pentaethylenehexamine, and diethylenetriamine. R ₁ -NH ₂ and R ₁ -N (R ₂ ) H and R ₁ -N (R ₂ ) -R ₃ in it will be possible to use at least any one or more of any type of amine (amine) is a functional group-containing acids.

2 shows amines having a carbon dioxide adsorption function according to an embodiment of the present invention.

The curing agent may be a polyfunctional epoxy material such as poly (ethylene glycol) diglycidyl ether, 1,4-butanediyl diglycidyl ether, 3- [Bis (glycidyloxymethyl) methoxy] -1,2-propanediol, diglycidyl 1,2-cyclohexanedicarboxylate, (Ethylene-co-glycidyl methacrylate) and poly (ethylene-co-glycidyl methacrylate), which are unicellular substances of A diglycidyl ether, Tris (4-hydroxyphenyl) methane triglycidyl ether and Tetra-Functional Epoxy Resin -methyl acrylate-co-glycidyl methacrylate) copolymerizable polymer material.

Figure 3 shows various curing agents for amine adsorbents according to embodiments of the present invention.

Preparing an amine and a curing agent; stirring the amine and the curing agent to prepare a mixture; dissolving the amine in an organic solvent; dissolving the curing agent in an organic solvent; It would be possible to further include steps.

In the step of preparing the mixture by stirring the amine and the curing agent, the ratio of the curing agent: amine may preferably be in a weight ratio of 1: 1 to 1:20.

More preferably, the ratio of the curing agent: amine is 1: 3 to 1: 6 by weight, but is not limited thereto.

It may be preferable to carry out the reaction at 60 ° C to 120 ° C for 4 hours to 36 hours in the step of placing the mixture prepared by stirring the amine and the curing agent into an oven and reacting.

Most preferably, the reaction is carried out at 80 DEG C for 24 hours, but is not limited thereto.

After the completion of the reaction, the unreacted material is removed using methanol, and then dried in a temperature range of 30 ° C to 80 ° C or in a range of 1 to 10 ^-7 torr ≪ / RTI >

FIG. 13 shows a method for producing a carbon dioxide (CO ₂ ) adsorbing material using a crosslinking reaction of an amine according to another embodiment of the present invention.

Another method for producing a carbon dioxide (CO ₂ ) adsorbent material using a crosslinking reaction of an amine includes the steps of preparing an amine, a curing agent and a polymer, mixing the amine and the curing agent Preparing a second mixture by further adding the polymer to the first mixture, melt mixing the second mixture with a twin extruder to prepare a molten mixture, And a step of cooling the molten mixture to complete the master batch by cutting to a predetermined size.

The amine is an amine containing at least one functional group selected from the group consisting of R ₁ -NH ₂ , R ₁ -N (R ₂ ) H and R ₁ -N (R ₂ ) -R _3. Polyethylenimine, Tetraethylenepentamine , Triethylenetetramine, pentaethylenehexamine, and diethylenetriamine, but is not limited thereto. R ₁ -NH ₂ and R ₁ -N (R ₂ ) H and R ₁ -N (R ₂ ) -R ₃ in it will be possible to use at least any one or more of any type of amine (amine) is a functional group-containing acids.

The curing agent may be a polyfunctional epoxy material such as poly (ethylene glycol) diglycidyl ether, 1,4-butanediyl diglycidyl ether, 3- [Bis (glycidyloxymethyl) methoxy] -1,2-propanediol, diglycidyl 1,2-cyclohexanedicarboxylate, (Ethylene-co-glycidyl methacrylate) and poly (ethylene-co-glycidyl methacrylate), which are unicellular substances of A diglycidyl ether, Tris (4-hydroxyphenyl) methane triglycidyl ether and Tetra-Functional Epoxy Resin -methyl acrylate-co-glycidyl methacrylate), but it is not limited thereto.

The polymer may include at least one of polypropylene (PP), high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).

Most preferably, at least one of PP (polypropylene) and LDPE (low density polyethylene) is used, but the present invention is not limited thereto.

In addition to this, it is also possible to select from commercially available polymers.

In the step of preparing the first mixture by mixing the amine with the curing agent, the ratio of the curing agent: amine may preferably be in a weight ratio of 1: 1 to 1:20.

More preferably, the ratio of the curing agent to the amine is from 1: 3 to 1: 6 by weight, but is not limited thereto.

In the step of preparing the second mixture by further adding the polymer to the first mixture, it is preferable that the ratio of the first mixture: the polymer is 1: 0.5 to 1: 1.5 by weight.

More preferably, the ratio of the first mixture to the polymer is 1: 1 by weight, but is not limited thereto.

In the step of melt-mixing the second mixture with a twin extruder to prepare a molten mixture, it is preferable to melt-mix at 150 ° C to 250 ° C.

More preferably, when LDPE is used as the polymer, the working temperature is preferably set to 180 ° C. When PP is used as the polymer, it is preferably set to 200 ° C.

The rotational speed of the main section of the twin extruder is preferably set to 250 rpm and the feeder is set to 85 rpm, but is not limited thereto.

Adding the polymer to the master batch after the completion of the master batch by cutting to a predetermined size by cooling the molten mixture and then melt mixing the mixture with a twin extruder May be further included.

FIG. 4 is a schematic view showing the preparation of a completely organic carbon dioxide adsorbent prepared by curing an amine adsorbent according to an embodiment of the present invention.

The carbon dioxide produced by the method of any one of the method of the present invention (CO ₂₎ the carbon dioxide production, including adsorption material (CO ₂₎ absorbent is characterized in that it does not contain an inorganic material.

That is, by adding a curing agent into a large amount of amine and reacting it, the amine that maintains a liquid state at room temperature is partially crosslinked to transform it into a solid polymer. When the amine is solidified, an inorganic material carrier such as silica or Aerosil is unnecessary and can be directly blended with a desired polymer resin.

In this way, a cured amine of a three-dimensional network structure is formed through a mutual reaction between a fluid amine chain and a cross linker having an epoxy functional group. In this case, by appropriately controlling the amount of the curing agent, Viscosity and hardness can be adjusted.

That is, the carbon dioxide (CO ₂ ) adsorbent produced by the present invention does not require a carrier such as mesoporous silica and does not dissolve in water and organic solvent due to the cross-linking reaction of the amine, It is possible to manufacture a carbon dioxide adsorbing material capable of performing blending, extrusion, injection molding, and the like, thereby overcoming all the problems of the conventional adsorbent.

To do this the system carbon dioxide (CO ₂₎ adsorption method using a (CO ₂₎ absorbent is characterized in that 35 ℃ to carbon dioxide at 90 ℃ (CO ₂₎ adsorbed by the adsorption rate of the carbon dioxide (CO ₂₎ is 50% to 90% do.

The reaction time is from 1 hour to 3 hours, most preferably 2 hours, but not limited thereto.

The crosslinking reaction was carried out by mixing PEGDE (poly (ethylene glycol) diglycidyl ether) and PEI (Polyethyleneimine) (Mn = 10,000) (PEI (10K)) in various composition ratios. 1 g of PEGDE and 10 g of PEI (10K) were well mixed and placed in an oven at 80 DEG C for reaction for 24 hours.

After the reaction was completed, unreacted material was removed using methanol and vacuum dried. The crosslinked PEI (C-PEI) was analyzed by FT-IR and TGA analysis for molecular structure and carbon dioxide adsorption.

PEGDE  (g) PEI  10K (g) yield(%) One 3 83.5 5 87.8 6 85.4 7 84.1 10 85.9 20 78.4

Table 1 summarizes the production results of C-PEI prepared by mixing PEGDE and PEI 10K at various mass ratios. All samples except for CPEI prepared at a weight ratio of 1:20 were obtained in a yield of 80% or more. The reason for the decrease in yield at 1:20 is that the amount of PEI relative to PEGDE is relatively large, so that the PEI which is not highly crosslinked or crosslinked is washed away in methanol in the washing step.

FT-IR analysis was carried out to confirm the structure of C-PEI prepared at each weight ratio, and it is shown in FIG. In the spectrum of PEGDE, the characteristic peak of the epoxy functional group appears at 908 cm ^-1 .

It can be seen that this characteristic peak disappeared from all samples through a crosslinking reaction with PEI.

6 shows an electron transmission microscope (TEM) photograph of C-PEI (1: 3) and C-PEI (1: 6).

TEM images show no difference between the two materials and no pores can be identified in the two adsorbents.

A scanning electron microscope (SEM) analysis was performed to identify the surface of C-PEI (1: 6) and the results are shown in FIG.

As seen in the SEM, C-PEI (1: 6) has a fairly rough surface and it is difficult to find traces of pores on the surface when photographed at high magnification.

That is, in C-PEI (1: 6), there is no pores having a size of several tens of nanometers, such as mesopores, and the surface area of the polymer can be expected to increase by increasing the surface area.

Sample
Name PEGDE / PEI CO ₂ adsorption Max .
( mg CO ₂  / g Sorbent ) CO ₂ adsorption Max .
( mmol CO ₂  / g Sorbent ) Weight
composition
(g / g) Molar
composition
( mol / mol ) C- PEI  (1: 2) 0.5 9.5 98.41 2.24 C- PEI  (1: 3) 0.33 6.33 186.78 4.25 C- PEI  (1: 6) 0.17 3.17 129.28 2.94 C- PEI  (1:10) 0.1 1.9 93.12 2.12 C- PEI  (1:20) 0.05 0.95 39.51 0.90

The carbon dioxide adsorption performance of each sample was analyzed. The maximum amount of carbon dioxide adsorbed is shown in Table 2. Each adsorption value shown in Table 2 is a value measured when it is exposed to carbon dioxide for 120 minutes under the condition of 75 ° C. C-PEI 1: 3 adsorbs 186.78 mg of carbon dioxide per g-adsorbent, which is interpreted to be similar to the adsorption amount of the adsorbent physically impregnated with well-known mesoporous silica PEI.

FIG. 8 shows a graph of carbon dioxide adsorption over time of C-PEI 1: 2, 1: 3, and 1: 6. As shown in the figure, C-PEI (1: 3) shows 160 mg or 90% carbon dioxide adsorption during the initial 20 minutes.

By comparison, C-PEI (1: 2) for the adsorption performance falls to half of which is -NH ₂ functional groups of the PEI molecules are relatively Crosslinker (PEGDE) of the large amount used, due to the crosslinking reaction has run out adsorption of carbon dioxide This is because the site has been reduced. Also, it can be seen that even when the crosslinker is relatively used, the adsorption performance is low.

9 is a graph showing the carbon dioxide adsorption performance of C-PEI (1: 3) and C-PEI (1: 6) at room temperature (35 ° C). As a result, the maximum absorption value of C-PEI (1: 3) was 22.49 mg / g-sorbent and that of C-PEI (1: 6) was 24.23 mg, which indicates that the adsorption performance was significantly lower than that measured at 75 ° C .

On the other hand, the adsorption performance of C-PEI (1: 3), which showed superior performance at 75 ° C, decreased sharply at 35 ° C and showed an adsorption value similar to that of C-PEI (1: 6) Is drastically reduced at low temperatures. In other words, the optimum mixing ratio range of PEI (10K) and crosslinker is 3 to 6 times the optimum PEI based on the cross linker.

KDT-4400 (National Highway) with four epoxy functional groups was stirred in dimethylformamide (DMF) until fully dissolved and PEI (Mn = 10,000) (PEI (10K)) was dissolved in methanol and the two solutions were mixed The crosslinking reaction proceeded as follows. 2.5 g of KDT-4400 was dissolved in 4 g of dimethylformamide (DMF), and 10 g of PEI (10 K) was dissolved in 20 g of methanol. The solutions were well mixed using a stirrer, and then placed in an oven at 80 ° C. for 24 hours .

After the reaction was completed, unreacted material was removed using methanol and vacuum dried.

The amount of carbon dioxide adsorption was measured using TGA analysis.

PEI  10K (g) KDT -4400 (g) Yield (%) CO ₂ adsorption  Max.
( mg CO ₂  / g Sorbent ) 10 1.25 86.6 100.1 1.85 87.9 101.3 2.5 88.1 95.4 3.1 87.9 89.7 3.75 86.5 88.1

Table 3 shows the production results of C4-PEI prepared by mixing KDT-4400 and PEI 10K at various mass ratios and the maximum carbon dioxide adsorption amount.

The yield of all the samples was close to 90%, which can be interpreted as the reason that the probability of reaction with PEI 10K is high because there are four functional groups of KDT-4400.

In addition, the form of the product is obtained as a harder solid, unlike the case of PEGDE, which appears to be attributed not only to the number of functional groups of KDT-4400 but also to the strong phenyl group on the molecular structure.

The stronger the hardness, the easier it is to grind into the powder type, which is advantageous for secondary processing. For example, when the particles are too large in the commercial polymer, the compounding is not good and problems occur in the properties of the master batch to be produced.

That is, the finer the particles are, the better the compatibility with the polymer and advantageous for producing the master batch. In the case of the maximum carbon dioxide adsorption amount, it is seen that the higher the relative content of KDT-4400 is, the more the amount of the amine to participate in the curing reaction with the epoxy increases.

A carbon dioxide adsorption master batch was produced by a continuous process using a twin extruder. The procedure was as follows.

10 shows a schematic diagram of a twin extruder process in an embodiment of the present invention.

 A 58 mm twin extruder from SM Platech (Korea) was used. LDPE 963 of Hanwha Chemical and PP J-160 of Honam Petrochemical were used as the polymer used in the production.

When LDPE is used, the working temperature is set at 180 ° C, and when PP is used, it is set at 200 ° C.

The extruder main rotation speed was set to 250 rpm and the feeder was set to 85 rpm.

2.5 kg of PEGDE in liquid form and 15 kg of PEI 10K are mixed in bulk in a vessel.

Add 17.5 kg of powder type polypropylene (PP) into the liquid mixture and mix well.

This facilitates incorporation into the inlet of the twin extruder and makes the melt mixing of PEI10K, PEGDE and PP constant.

The prepared mixed material was gradually injected into a twin extruder inlet preheated to 200 캜 and melt-mixed at a speed of 250 rpm.

The molten mixed material discharged from the twin extruder is cooled and then cut to a certain size to complete the master batch.

The color of the completed master batch is yellow and its shape is shown in Fig.

The masterbatch prepared by mixing carbon dioxide adsorbing material and PP at a ratio of 50:50 can be melt-mixed with a commercial polymer using Twin Extruder again.

The production process of the PP master batch of C-PEI and C4-PEI using twin extruder is as follows.

The solid state C-PEI was pulverized into a powder form using a pulverizer. 5 kg of well-pulverized C-PEI and 5 kg of PP are slowly mixed with the inlet of the twin extruder and melt mixed at 180 ° C and 200 rpm.

The molten mixed material was cooled and then cut to a certain size to prepare a master batch. The C4-PEI master batch was also prepared by the same procedure.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it should be understood that various changes and modifications will be apparent to those skilled in the art. It is to be understood that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.

Claims (19)

delete delete delete delete delete delete delete A method for producing a carbon dioxide (CO ₂ ) adsorbent material using a crosslinking reaction of an amine,
(a) preparing an amine, a curing agent and a polymer;
(b) mixing the amine with the curing agent to prepare a first mixture;
(c) further adding the polymer to the first mixture to produce a second mixture;
(d) melt mixing the second mixture with a twin extruder to prepare a molten mixture;
(e) cooling the molten mixture to a predetermined size to complete a master batch;
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine. The method of claim 8,
The amine is an amine containing at least one functional group selected from the group consisting of R ₁ -NH ₂ , R ₁ -N (R ₂ ) H and R ₁ -N (R ₂ ) -R _3. Polyethylenimine, Tetraethylenepentamine , Triethylenetetramine, pentaethylenehexamine, and diethylenetriamine.
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, The method of claim 8,
The curing agent is a polyfunctional epoxy material selected from the group consisting of poly (ethylene glycol) diglycidyl ether, 1,4-butanediyl diglycidyl ether, 3- [Bis (glycidyloxymethyl) methoxy] -1,2-propanediol, diglycidyl 1,2-cyclohexanedicarboxylate, bisphenol A diglycidyl ether, Tris (4-hydroxyphenyl) methane triglycidyl ether and Tetra-Functional Epoxy Resin (KDT-4400), o-Cresol Novolac, Poly (ethylene-co-glycidyl methacrylate) acrylate-co-glycidyl methacrylate).
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, The method of claim 8,
The polymer
And at least one of PP (Polypropylene), HDPE (High Density Polyethylene), LDPE (Low Density Polyethylene) and LLDPE (Linear Low Density Polyethylene)
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, The method of claim 8,
In the step (b)
The ratio of the curing agent: amine is 1: 1 to 1:20 by weight
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, The method of claim 8,
In the step (c)
The ratio of the first mixture: the polymer is 1: 0.5 to 1: 1.5 by weight
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, The method of claim 8,
In the step (d)
Melting and mixing at 150 캜 to 250 캜
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, The method of claim 8,
After the step (e)
Further adding the polymer to the master batch and further melt mixing the mixture with a twin extruder
(CO ₂ ) adsorbing material using a cross-linking reaction of an amine, delete delete In the carbon dioxide (CO ₂₎ absorbent,
It includes a carbon dioxide (CO ₂₎ adsorption material prepared by any of the methods of claims 8 to 15,
Does not contain inorganic materials
(CO ₂ ) adsorbent. In the carbon dioxide (CO ₂₎ absorption method using the carbon dioxide (CO ₂₎ absorbent,
(CO ₂ ) adsorbent of claim 18,
Carbon dioxide (CO ₂ ) is adsorbed at 35 ° C to 90 ° C,
Those having an adsorption rate of carbon dioxide (CO ₂ ) of 50% to 90%
(CO ₂ ) adsorption method.

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